CN112390811B - Dithia-anthrone derivative and preparation method and application thereof - Google Patents

Abstract

The invention discloses a dithiaanthrone derivative, a preparation method thereof and application thereof in an electroluminescent device. The structural general formula of the dithiaanthrone derivative is shown as a formula I and a formula II:

wherein X is selected from a sulfur atom or a sulfone group; r₁、R₂、R₃、R₄And R₅Each independently selected from a hydrogen atom, an arylamine group of 6 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a substituted heteroaromatic group of 5 to 50 ring atoms. The oxidized and unoxidized dithianone derivatives of the invention introduce various electron donating groups, realize effective donor-acceptor type molecular design, can effectively separate the highest occupied orbital energy level and the lowest vacant orbital energy level of molecules, reduce the energy level difference between singlet state and triplet state, and realize thermal activation delayDelayed fluorescence properties, enabling luminescence of different colors. The organic electroluminescent device is applied to a luminescent layer of the organic electroluminescent device, and the device has excellent performance.

Description

Dithia-anthrone derivative and preparation method and application thereof

Technical Field

The invention relates to the technical field of organic electroluminescent display. More particularly, relates to a dithianone derivative, a synthesis preparation method thereof and application of an organic electroluminescent device.

Background

The Organic Light-Emitting material directly affects the device performance of an Organic Light-Emitting Diode (OLED) as one of indispensable important components in the OLED device. Although fluorescent light emitting materials exhibit excellent stability, the Internal Quantum Efficiency (IQEs) of fluorescent OLED devices is limited to 25%, resulting in undesirable device performance for such devices. OLED devices based on phosphorescent emitters are capable of 100% exciton utilization under electrical excitation. However, the introduction of expensive transition metals into phosphorescent materials increases the device fabrication cost, and in addition, phosphorescent OLED devices have problems of severe efficiency roll-off and lack of high-performance blue light emitting materials, which limit their applications. In order to overcome the above disadvantages, TADF (thermally activated delayed fluorescence) can achieve 100% exciton utilization rate, has become a third-generation organic electroluminescent material, and has a wide application prospect in the future OLED field.

It has been reported before that the thermal activation delayed fluorescence luminescent material based on thioxanthone derivative shows excellent luminescent performance when applied to OLED devices, but the luminescent position is in yellow and orange regions, thus the luminescent material can not realize luminescence at different positions and is not suitable for preparing white OLED devices with high color rendering index. Therefore, it is desirable to provide an organic thermally activated delayed fluorescence light emitting material having a wider light emitting region and higher charge transport properties that can be applied in a white OLED device.

Disclosure of Invention

The first purpose of the invention is to provide a dithianone derivative, which has a dithianone acceptor unit and different donor groups, and is beneficial to improving the charge transport capacity of the material and realizing different colors of luminescence.

The second purpose of the invention is to provide a synthetic method of the dithiaanthrone derivative.

The third purpose of the invention is to provide the application of the dithiaanthrone derivative.

In order to achieve the first purpose, the invention adopts the following technical scheme:

the invention provides a dithiaanthrone derivative, which has a structural general formula shown as a formula I and a formula II:

wherein X is selected from a sulfur atom or a thiosulfone group; r₁、R₂、R₃、R₄And R₅Each independently selected from a hydrogen atom, an arylamine group of 6 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a substituted heteroaromatic group of 5 to 50 ring atoms.

The dithianone derivative is prepared by carrying out novel molecular design on thioxanthone and realizing the structural design of the dithianone through a condensed ring strategy. On one hand, the condensed ring strategy increases the electron-withdrawing ability and the conjugation degree, so that the light emitted by the compound can generate effective red shift, and the light emission in deep red and near infrared regions is realized; on the other hand, the method is beneficial to improving the transmission performance of holes and electrons. Therefore, the dithranone derivative modified with substituents with different electron donating capacities, provided by the invention, can effectively adjust the optical band gap, so that different colors of luminescence can be realized, and the dithranone derivative has great potential in the application of pure color OLED devices and white light OLED devices.

Specifically, a plurality of electron-rich groups are introduced, so that the dithianone derivative provided by the invention has certain electron transport capacity, and the highest occupied orbital (HOMO) energy level and the lowest unoccupied orbital (LUMO) energy level of the dithianone derivative can be effectively separated through group modification of different electron donating capacities, so that the energy level difference between a singlet state and a triplet state is reduced, and light emission of different colors is realized.

In addition, the invention adjusts the photophysical properties of the substance, such as luminous color, luminous efficiency, intramolecular charge transfer and the like by introducing aryl, substituted aryl, arylamine and heterocyclic aryl with different electron donating abilities.

Preferably, the arylamine group having 6 to 30 carbon atoms is at least one selected from the group consisting of a diphenylamine group, a triphenylamine group, a methylphenylamine group, an ethylphenylamine group, a propylphenylamino group, an isopropylphenylamino group, an ethoxyphenylamino group, a propoxyphenylamine group, a fluorophenylamine group, a chlorophenylamine group, a bromophenylamino group, an iodophenylamino group, a dimethylphenylamino group, a diethylphenylamino group, a dipropylphenylamine group, a diisopropylphenylamino group, a dimethoxyphenylamino group, a diethoxyphenylamine group, a dipropoxyphenylamine group, a difluorophenylamino group, a dichlorophenylamino group, a dibromophenylamino group, and a diiodophenylamino group, and the substituent of the phenyl group includes an ortho-para position.

Preferably, the aryl group having 6 to 30 carbon atoms is selected from at least one of phenyl, perylenyl, pyrenyl, fluorenyl, spirobifluorenyl, diphenyl, triphenyl, tetracenyl and 9, 9' -spirobifluorenyl.

Preferably, the substituted aryl group of 6 to 30 carbon atoms is selected from at least one of o-tolyl, m-tolyl, p-tolyl, xylyl, o-cumyl, m-cumyl, p-cumyl, trimethylphenyl, and 9, 9' -dimethylfluorenyl.

Preferably, the heterocyclic aryl group of 5 to 50 carbon atoms is selected from the group consisting of 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, p-benzofuryl, 7-benzofuranyl, dibenzofuran-2-yl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, N-phenylcarbazolyl, 1-phenazine group, 2-phenazine group, 3-phenazine group, 4-phenazine group, 6-phenazine group, 7-phenazine group, 8-phenazine group, 9-phenazine group, 10-phenazine group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9, 10-dimethylazinyl group, 1, 7-phenaline-2-yl group, 1, 7-phenaline-3-yl group, 1, 7-phenaline-4-yl group, 1, 7-phenaline-5-yl group, 1, 7-phenaline-6-yl group, 1, 7-phenaline-8-yl group, 1-phenaline-3-yl group, 1, 7-phenaline-4-yl group, 1, 7-phenaline-5-yl group, 1, 7-phenaline-6-yl group, 1, 7-phenaline-8-yl group, 1, 7-phenanthroline-9-yl group, 1, 7-phenanthroline-10-yl group, 1, 8-phenanthroline-2-yl group, 1, 8-phenanthroline-3-yl group, 1, 8-phenanthroline-4-yl group, 1, 8-phenanthroline-5-yl group, 1, 8-phenanthroline-6-yl group, 1, 8-phenanthroline-7-yl group, 1, 8-phenanthroline-9-yl group, 1, 8-phenanthroline-10-yl group, 1, 9-phenanthroline-2-yl group, 1, 9-phenanthroline-3-yl group, 1, 9-phenanthroline-4-yl group, 1, 9-phenanthroline-5-yl group, 1, 9-phenanthroline-6-yl group, 1, 9-phenanthroline-7-yl group, 1, 9-phenanthroline-8-yl group, 1, 9-phenanthroline-10-yl group, 1, 10-phenanthroline-2-yl group, 1, 10-phenanthroline-3-yl group, 1, 10-phenanthroline-4-yl group, 1, 10-phenanthroline-5-yl group, 2, 9-phenanthroline-1-yl group, 2, 9-phenanthroline-3-yl group, 2, 9-phenanthroline-4-yl group, 2, 9-phenanthroline-5-yl group, 2, 9-phenanthroline-6-yl group, 2, 9-phenanthroline-7-yl group, 2, 9-phenanthroline-8-yl group, 2, 9-phenanthroline-10-yl group, 2, 2, 8-phenanthroline-1-yl, 2, 8-phenanthroline-3-yl, 2, 8-phenanthroline-4-yl, 2, 8-phenanthroline-5-yl, 2, 8-phenanthroline-6-yl, 2, 8-phenanthroline-7-yl, 2, 8-phenanthroline-9-yl, 2, 8-phenanthroline-10-yl, 2, 7-phenanthroline-1-yl, 2, 7-phenanthroline-3-yl, 2, 7-phenanthroline-4-yl, 2, 7-phenanthroline-5-yl, 2, 7-phenanthroline-6-yl, 2, 7-phenanthroline-8-yl, 2, 7-phenanthroline-9-yl, 2, 7-phenanthroline-10-yl, 1-phenothiazinyl, 2-phenazinyl, phenothiazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, phenoxazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl, dibenzothiophen-2-yl.

In order to achieve the second purpose of the invention, the following technical scheme is provided:

a synthetic method of dithiaanthrone derivatives comprises the following steps:

when the dithiaanthrone derivative has the general structural formula as shown in formula I:

when R is₁、R₃Is a hydrogen atom, R₂When not hydrogen atom, the synthesis method comprises the following steps: : a compound of formula a and a compound having R₂Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₂Carrying out Ullmann reaction on a nitrogen-containing heterocyclic compound of a substituent group to obtain a compound with a structural formula shown as a formula I-1;

or

When R is₁Is a hydrogen atom, R₂、R₃When not hydrogen atom, the synthesis method comprises the following steps: : mixing the compound shown as the formula I-1 with liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula b(ii) a A compound of the formula b and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-2;

or

When R is₁Not being a hydrogen atom, R₂、R₃When the hydrogen atom is used, the synthesis method comprises the following steps: a compound of the formula c and a compound having R₁Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₁Carrying out Ullmann reaction on a nitrogen-containing heterocyclic compound of a substituent group to obtain a compound with a structural formula shown as a formula I-3;

or

When R is₁、R₃Not being a hydrogen atom, R₂When the hydrogen atom is used, the synthesis method comprises the following steps: mixing the compound shown as the formula I-3 and liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula d; compounds of formula d and having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₁Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-4;

or

When R is₁、R₂、R₃And when the hydrogen atom is taken as the hydrogen atom, the structure of the compound shown in the formula I is shown as the formula I-5:

wherein, when X is a sulfur atom, the synthesis method comprises the following steps:

reacting to generate a compound shown as a formula I-5-1,

when X is a sulfosulfonyl group, the synthesis method comprises the following steps:

dissolving the compound shown as the formula I-5-1 in dichloromethane under the condition of ice-water bath, adding m-chloroperoxybenzoic acid, reacting at room temperature to obtain the compound shown as the formula I-5-2,

or

When R is₁、R₂And at the same time being a hydrogen atom, R₃When not hydrogen atom, the synthesis method comprises the following steps: : mixing the compound shown as the formula I-5 and liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula e; a compound of the formula e and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-6;

or

When R is₁、R₂While not being a hydrogen atom, R₃When the hydrogen atom is used, the synthesis method comprises the following steps: : a compound of the formula f with a compound having R₂Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₂Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula g; a compound of the formula g with a compound having R₁Suzuki reaction of substituted boronic acid or boronic acid pinacol esterOr with a radical R₁Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula I-7,

or

When R is₁、R₂、R₃Meanwhile, when the hydrogen atom is not contained, the synthesis method comprises the following steps: mixing the compound shown as the formula I-7 with liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula h; a compound of the formula h and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula I-8,

when the dithiaanthrone derivative has the general structural formula as described in formula II:

when R is₄、R₅And when the hydrogen atom is taken as the hydrogen atom, the structure of the compound shown in the formula I is shown as a formula II-1:

wherein, when X is a sulfur atom, the synthesis method comprises the following steps:

reacting to generate a compound shown as a formula II-1-1:

when X is a sulfosulfonyl group, the synthesis method comprises the following steps:

dissolving the compound shown as the formula II-1-1 in dichloromethane under the condition of ice-water bath, adding m-chloroperoxybenzoic acid, reacting at room temperature to obtain the compound shown as the formula II-1-2,

or

When R is₄Not being a hydrogen atom, R₅When the hydrogen atom is used, the synthesis method comprises the following steps: a compound of formula i with a compound having R₄Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₄Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula II-2,

or

When R is₄Is a hydrogen atom, R₅When not hydrogen atom, the synthesis method comprises the following steps: compounds of formula j and having R₅Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₅Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula II-3,

or

When R is₄、R₅Meanwhile, when the hydrogen atom is not contained, the synthesis method comprises the following steps: : compounds of formula k and having R₄Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₄Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula l; a compound of formula I with a compound having R₅Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with substituted boronic acid pinacol esterHas R₅Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula II-4,

as mentioned above, the process for synthesizing dithio-xanthone derivatives provided by the invention comprises bromo-dithio-xanthone acceptor unit and R₁、R₂、R₃、R₄、R₅Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with boronic acid pinacol ester with R₁、R₂、R₃、R₄、R₅And (3) carrying out Ullmann reaction on the substituted nitrogen-containing heterocyclic compound.

Wherein said has R₁、R₂、R₃、R₄、R₅The structural formula of the boric acid and the pinacol borate of the substituent group is as follows:

further, the Suzuki reaction is that bromo-dithianon acceptor and R are carried₁、R₂、R₃、R₄、R₅Adding the pinacol borate of the substituent group into a mixed solution of palladium tetratriphenylphosphine and potassium carbonate as catalysts and toluene and water as solvents, refluxing under the protection of nitrogen, removing the solvents, extracting, and evaporating to dryness.

Preferably, the refluxing time is 3-5 h; the reaction is incomplete when the time is too short, and energy is wasted when the time is too long.

Further, the Ullmann reaction is that bromo-dithianone acceptor and R-bearing₁、R₂、R₃、R₄、R₅Adding catalyst palladium acetate, tri-tert-butylphosphine tetrafluoroborate, alkali sodium tert-butoxide and solvent anhydrous toluene into the nitrogen-containing heterocyclic compound of the substituent group, refluxing under the protection of nitrogen, removing the solvent, extracting and evaporating to dryness to obtain the compound.

Preferably, refluxing for 16-24 h; the reaction is incomplete when the time is too short, and energy is wasted when the time is too long.

The synthetic method of the dithiaanthrone derivative provided by the invention is simple and convenient, is easy to operate, and the obtained dithiaanthrone derivative has good performance.

Furthermore, the brominated dithianone acceptor unit provided by the invention is prepared according to the method in the prior art aiming at the difference of sulfur atoms and sulfone groups.

Preferably, when X is a sulfur atom,

the synthesis process of the compound shown in the formula a is as follows:

the synthesis process of the compound shown in the formula c is as follows:

the synthesis process of the compound shown as the formula I-5-1 comprises the following steps:

the synthesis process of the compound shown in the formula f is as follows:

the synthesis process of the compound shown in the formula II-1-1 comprises the following steps:

the synthesis process of the compound shown in the formula i comprises the following steps:

the synthesis process of the compound shown in the formula j comprises the following steps:

the synthesis process of the compound shown in the formula k is as follows:

when X is a thiosulfonyl group, the compounds shown in formula a, formula c, formula f, formula i, formula j and formula k are respectively:

the compounds shown in the formula a-2, the formula c-2, the formula f-2, the formula i-2, the formula j-2 and the formula k-2 are obtained by respectively dissolving the compounds shown in the formula a-1, the formula c-1, the formula f-1, the formula i-1, the formula j-1 and the formula k-1 in dichloromethane under the condition of ice-water bath, adding m-chloroperoxybenzoic acid, and reacting at room temperature.

In the compounds shown in the formula I and the formula II, X is selected from a sulfur atom and a thiosulfonyl group. In the specific preparation process, when X is a sulfur atom, the synthesis process is as follows: synthesizing a dithio-xanthone acceptor unit with a halogen substituent group and X as a sulfur atom from raw materials, and then preparing the dithio-xanthone derivative with X as the sulfur atom through a Suzuki reaction or a Ullmann reaction. When X is a sulfosulfonyl group, the synthesis process has two options: synthesizing a dithio-thioxanthone acceptor unit with a halogen substituent group and X as a sulfur atom from raw materials, then preparing a dithio-thioxanthone derivative with X as the sulfur atom by Suzuki reaction or Ullmann reaction, dissolving the dithio-thioxanthone derivative containing the sulfur atom in dichloromethane under the condition of ice-water bath, then adding m-chloroperoxybenzoic acid, and reacting at room temperature to obtain the dithio-thioxanthone derivative containing a thiosulfone group; synthesizing a dithio-heteroanthrone acceptor unit with a halogen substituent and X as a sulfur atom from raw materials, dissolving the dithio-heteroanthrone acceptor unit in dichloromethane under the condition of ice-water bath, then adding m-chloroperoxybenzoic acid, reacting at room temperature to obtain the dithio-heteroanthrone acceptor unit substituted by the halogen and containing a thiosulfonyl group, and then preparing the dithio-heteroanthrone derivative with X as the thiosulfonyl group through Suzuki reaction or Ullmann reaction.

In the synthesis process of the compounds shown in the formula a-1, the formula c-1, the formula I-5-1 and the formula f-1, the reaction is divided into three steps:

the first step is to mix the compound

Dissolving sodium hydride in ultra-dry N, N-Dimethylformamide (DMF), vacuumizing, introducing nitrogen, and adding another raw material

Heating the DMF solution for reaction, adding water, filtering and carrying out column chromatography to obtain a first intermediate product;

dissolving the intermediate product 1 and potassium hydroxide in an ethanol water solution, heating for reaction until the intermediate product is clear, cooling to room temperature, adding acid, precipitating, filtering, and drying to obtain a second intermediate product;

and thirdly, dissolving the intermediate product 2 in concentrated sulfuric acid, heating for reaction, pouring the reaction solution into ice water, separating out a precipitate, and purifying to obtain the product.

In the synthesis process of the compounds shown in the formula II-1-1, the formula i-1, the formula j-1 and the formula k-1, provided by the invention, the reaction is divided into three steps:

the first step is to mix the compound

Dissolving sodium hydride in ultra-dry N, N-Dimethylformamide (DMF), vacuumizing, introducing nitrogen, and addingAdding another raw material

Heating the DMF solution for reaction, adding water, filtering and carrying out column chromatography to obtain a third intermediate product;

dissolving the intermediate product 3 and potassium hydroxide in an ethanol water solution, heating for reaction until the intermediate product is clear, cooling to room temperature, adding acid, precipitating, filtering, and drying to obtain a fourth intermediate product;

and thirdly, dissolving the intermediate product 4 in concentrated sulfuric acid, heating for reaction, pouring the reaction solution into ice water, separating out a precipitate, and purifying to obtain the product.

The third purpose of the invention is to provide the application of the dithiaanthrone derivative in preparing organic electroluminescent devices.

Preferably, the organic electroluminescent device is an organic electroluminescent device based on thermally activated delayed fluorescence.

The dithio-xanthone acceptor unit is introduced into the dithio-xanthone derivative, so that the electron-withdrawing capability of the acceptor is effectively improved, the conjugation length of the acceptor unit is widened, and the electron and hole transport performance of the material is favorably improved.

Preferably, the organic electroluminescent device is a white organic electroluminescent device.

The emission spectrum half-peak width of the solid film prepared by the dithianone derivative is very wide, and the emission peak of part of materials is prolonged to a deep red/near infrared region, so that the dithianone derivative can be applied to a white light organic electroluminescent device and realizes high color rendering index.

Preferably, the dithianone derivative is applied to a light emitting layer of an organic electroluminescent device.

In a specific embodiment, the organic electroluminescent device has the following structure: substrate-ITO anode-hole transport layer-exciton electron blocking layer-organic light emitting layer-electron transport layer-cathode;

the organic light-emitting layer is a dithianone derivative shown in formula I and formula II or a mixture of the dithianone derivative shown in formula I and formula II and TPBi or a mixture of the dithianone derivative shown in formula I and formula II and 2 SPAc-PPM; the substrate is one of glass, polyester and polyimide compounds; the anode is one of indium tin oxide, zinc oxide, tin zinc oxide, gold, silver, copper, polythiophene/sodium polyvinyl benzene sulfonate and polyaniline; the hole transport layer and the exciton electron blocking layer are made of triarylamine materials; the electron transport layer is a nitrogen heterocyclic material; the cathode is an electrode layer formed by lithium, magnesium, calcium, strontium, aluminum or indium, or an alloy of one of the above and copper, gold or silver, or the above metal or alloy and metal fluoride alternately.

The invention has the following beneficial effects:

1. the dithranone derivative provided by the invention effectively improves the electron withdrawing capability of the acceptor by introducing the dithranone acceptor unit, widens the conjugation length of the acceptor unit, and is beneficial to improving the electron and hole transport performance of the material.

2. According to the dithianone derivative provided by the invention, a plurality of electron-rich groups are introduced, so that the dithianone derivative has certain electron transport capacity, and the highest occupied orbital (HOMO) energy level and the lowest unoccupied orbital (LUMO) energy level of the dithianone derivative can be effectively separated through group modification with different electron donating capacities, so that the energy level difference between a singlet state and a triplet state is reduced, and light emission of different colors is realized.

3. The emission spectrum half-peak width of the solid film prepared by the dithianone derivative is very wide, and the emission peak of part of materials is prolonged to a deep red/near infrared region, so that the dithianone derivative can be applied to a white light organic electroluminescent device and realizes high color rendering index.

4. The synthetic method adopted by the dithianone derivative is simple and convenient, the operation is easy, and the performance of the obtained dithianone derivative is good.

5. The organic electroluminescent device based on thermally activated delayed fluorescence prepared by using the dithianone derivative as a guest luminescent material has superior performances of high brightness and high efficiency.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 shows the fluorescence spectrum and phosphorescence spectrum at 77K of the dithianone derivative of example 8 of the present invention.

FIG. 2 shows the fluorescence spectrum and phosphorescence spectrum at 77K of the dithianone derivative of example 10 of the present invention.

FIG. 3 is a schematic structural diagram of an organic electroluminescent device based on thermally activated delayed fluorescence and white light, which is prepared by using the dithianone derivative of the present invention as a guest material.

Fig. 4 shows the electroluminescence spectra of organic electroluminescent devices based on Comp-2 and TPBi doping as the light-emitting layer according to example 30 of the present invention.

Fig. 5 shows current density and luminance curves at different voltages for organic electroluminescent devices based on Comp-2 and TPBi doping as light emitting layers according to example 30 of the present invention.

Fig. 6 shows the electroluminescence spectra of organic electroluminescent devices based on Comp-6 doped with TPBi as the light-emitting layer according to example 31 of the present invention.

Fig. 7 shows current density and luminance curves at different voltages for organic electroluminescent devices based on Comp-6 and TPBi doping as light emitting layers according to example 31 of the present invention.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.

Example 1

Synthesis of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione:

150mg of Compound 1, 180mg of Compound sodium hydride are dissolved in 10ml of ultra-dry N, N-Dimethylformamide (DMF), evacuated and purged with nitrogen. 500mg of Compound 2 was dissolved in 10ml of DMF, and added to the solution of Compound 1, and the reaction mixture was heated to 130 ℃ for 5 hours. The reacted solution was added with 100ml of water, the precipitate was filtered off, and column chromatography was carried out to obtain 438mg of product 3.

200mg of compound 3, 5g of potassium hydroxide, 10ml of water and 10ml of ethanol are mixed in a flask, the mixture is heated to 100 ℃ until the reaction solution becomes clear and then cooled to room temperature, excess hydrochloric acid is added to precipitate, the precipitate is filtered, and the mixture is dried in a vacuum drying oven to obtain 210mg of compound 4.

200mg of Compound 4 are dissolved in 10ml of concentrated sulfuric acid and reacted at 60 ℃ for 5 hours. Pouring the reaction solution into ice water, filtering out precipitate, and carrying out column chromatography to obtain 120mg of the product, namely the compound shown as the formula a-1. 1H NMR (400MHz, TFA) δ 9.46(d, J ═ 1.4Hz,2H),8.57(s,2H),8.42(dd, J ═ 8.7,1.5Hz,2H),8.16(d, J ═ 8.7Hz,2H), EIMS m/z (%): calcd for c 2H 20H8b 2o2s2, 503.83; 503.83 is Found.

Example 2

Synthesis of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione oxidation products: in an ice-water bath, 200mg of Compound a-1 was dissolved in 20ml of methylene chloride, 300mg was slowly added thereto, and the reaction mixture was allowed to cool to room temperature for overnight reaction. The reaction solution was concentrated and subjected to column chromatography to give 106mg of the product, a compound represented by the formula a-2. 1H NMR (400MHz, TFA) δ 8.22(s,2H),8.09(d, J ═ 1.5Hz,2H),7.93(dd, J ═ 7.5,1.5Hz,2H),7.75(d, J ═ 7.5Hz,2H), EIMS m/z (%): calcd for c20h8br2o6s2, 567.81; 567.81 is Found.

Example 3

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-1

Weighing 200mg of 2,9-dibromo thiochromeno [2,3-b ] thioxanthene-7, 14-dione and 650mg of 9-triphenylamine boric acid, adding the weighed materials into a 250mL double-opening bottle, adding 50mg of palladium tetrakistriphenylphosphine, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5 hours under the protection of nitrogen, removing the solvent under reduced pressure, extracting the mixture by using dichloromethane and water, combining organic phases, drying the solvent by evaporation under reduced pressure, and carrying out column chromatography to obtain the M-chloroperoxybenzoic acid-dithianone derivative Comp-1.

Example 4

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-2

Weighing 250mg of 2,9-dibromo thiochromeno [2,3-b ] thioxanthene-7, 14-dione oxidation product and 650mg of 9-triphenylamine boric acid into a 250mL double-mouth bottle, adding 50mg of tetrakistriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the dithiaanthrone derivative Comp-2.

Example 5

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-3

In the same manner as in example 3, 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was used in place of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione to obtain triphenylamine-substituted dithianone derivative Comp-3.

Example 6

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-4

In the same manner as in example 4, the oxidation product of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was replaced with the oxidation product of 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione to give triphenylamine-substituted dithianone derivative Comp-4.

Example 7

Synthesis of phenylcarbazole-substituted dithiaanthrone derivatives Comp-5

In the same manner as in example 3, 9-triphenylamine boronic acid was replaced with N-phenyl-3-carbazole boronic acid to obtain phenylcarbazole-substituted dithianone derivative Comp-5.

Example 8

Synthesis of phenylcarbazole-substituted dithiaanthrone derivatives Comp-6

In the same manner as in example 4, 9-triphenylamine boronic acid was replaced with N-phenyl-3-carbazole boronic acid to obtain phenylcarbazole-substituted dithianone derivative Comp-6.

FIG. 1 shows fluorescence spectrum and phosphorescence spectrum at low temperature 77K of photophysical data of Comp-6 prepared by the present invention, from which singlet and triplet energy levels of the compound can be calculated to determine its characteristics of thermally activated delayed fluorescence. The singlet level was 2.21eV, and the triplet level was 2.08 eV.

Example 9

Synthesis of phenylcarbazole-substituted dithiaanthrone derivatives Comp-7

In the same manner as in example 3, 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was used in place of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione, and N-phenyl-3-carbazolboronic acid was used in place of 9-triphenylamine boronic acid, so that benzenecarbazole-substituted dithianone derivative Comp-7 was obtained.

Example 10

Synthesis of phenylcarbazole-substituted dithiaanthrone derivatives Comp-8

In the same manner as in example 4, the oxidation product of 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione is used instead of the oxidation product of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione, and N-phenyl-3-carbazolboronic acid is used instead of 9-triphenylamine boronic acid, so that the phenylcarbazole-substituted dithianone derivative Comp-8 is obtained.

FIG. 2 shows fluorescence spectrum and phosphorescence spectrum at low temperature 77K of photophysical data of Comp-8 prepared by the present invention, from which singlet and triplet energy levels of the compound can be calculated to determine its characteristics of thermally activated delayed fluorescence. The singlet level was 2.25eV, and the triplet level was 2.19 eV.

Example 11

Synthesis of Diphenyl-substituted Dithia-Anthranone derivatives Comp-9

In the same manner as in example 3, diphenyl boronic acid was used instead of 9-triphenylamine boronic acid to obtain diphenyl-substituted dithianone derivative Comp-9.

Example 12

Synthesis of Diphenyl-substituted Dithia-Anthranone derivatives Comp-10

In the same manner as in example 4, diphenyl boronic acid was used instead of 9-triphenylamine boronic acid to obtain diphenyl-substituted dithianone derivative Comp-10.

Example 13

Synthesis of Diphenyl-substituted Dithia-Anthranone derivatives Comp-11

In the same manner as in example 3, 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was used in place of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione, and diphenylboronic acid was used in place of 9-triphenylamine boronic acid, whereby diphenyl-substituted dithianone derivative Comp-11 was obtained.

Example 14

Synthesis of Diphenyl-substituted Dithia-Anthranone derivatives Comp-12

In the same manner as in example 4, the oxidation product of 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was used in place of the oxidation product of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione, and diphenylboronic acid was used in place of 9-triphenylamine boronic acid, whereby the diphenyl-substituted dithianone derivative Comp-12 was obtained.

Example 15

Synthesis of carbazole-substituted dithiaanthrone derivative Comp-13

Weighing 2,9-dibromo thiochromeno [2,3-b ] thioxanthene-7, 14-dione and 382mg carbazole, adding the materials into a 100mL double-mouth bottle, adding 60mg PEPSI-Ipr catalyst, 98mg sodium tert-butoxide and 10mL anhydrous toluene solvent, carrying out reflux reaction for 24h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the carbazole-substituted dithiaanthrone derivative Comp-13.

Example 16

Synthesis of carbazole-substituted dithiaanthrone derivative Comp-14

Weighing 250mg of 2,9-dibromo thiochromeno [2,3-b ] thioxanthene-7, 14-dione oxidation product and 382mg of carbazole, adding the products and 382mg of carbazole into a 100mL double-mouth bottle, adding 60mg of PEPSI-Ipr catalyst, 98mg of sodium tert-butoxide and 10mL of anhydrous toluene solvent, carrying out reflux reaction for 24 hours under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the carbazole-substituted dithiaanthrone derivative Comp-14.

Example 17

Synthesis of carbazole-substituted dithiaanthrone derivative Comp-15

In the same manner as in example 15, 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was used in place of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione to obtain carbazole-substituted dithianone derivative Comp-15.

Example 18

Synthesis of carbazole-substituted dithiaanthrone derivative Comp-16

In the same manner as in example 16, the oxidation product of 2,9-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione was replaced with the oxidation product of 1, 7-dibromothiochromeno [2,3-b ] thioxanthene-7, 14-dione to give carbazole-substituted dithianone derivative Comp-16.

Example 19

Synthesis of phenylcarbazole-substituted dithiaanthrone derivative Comp-17

250mg comp-5 was added to a 150ml two-necked flask, 10ml glacial acetic acid was added, and then 1ml liquid bromine was added. The reaction mixture was heated to 120 ℃, reacted for 10 hours and then cooled to room temperature, and saturated sodium bisulfite solution was added to neutralize unreacted liquid bromine. Finally, filtration gave the bromo Comp-5 product.

Adding 200mg of bromo Comp-5 and 650mg of N-phenyl-3-carbazole boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, performing reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and performing column chromatography to obtain the dithiaanthrone derivative Comp-17.

Example 20

Synthesis of phenylcarbazole, triphenylamine substituted dithiaanthrone derivative Comp-18

In the same manner as in example 19, Comp-3 was used instead of Comp-5 to obtain bromo Comp-3, and finally phenylcarbazole and triphenylamine substituted dithianone derivative Comp-18 were obtained.

Example 21

Synthesis of 2, 9-dibromoothiochromeno [2,3-B ] thioxanthene-7, 14-dione Comp-19

150mg of Compound 5, 180mg of Compound sodium hydride are dissolved in 10ml of ultra-dry N, N-Dimethylformamide (DMF), evacuated and purged with nitrogen. 500mg of Compound 6 was dissolved in 10ml of DMF, and added to the solution of Compound 5, and the reaction mixture was heated to 130 ℃ for 5 hours. The reacted solution was added with 100ml of water, and the precipitate was filtered off and subjected to column chromatography to obtain 485mg of compound 7.

200mg of compound 7, 5g of potassium hydroxide, 10ml of water and 10ml of ethanol are mixed in a flask, the mixture is heated to 100 ℃ until the reaction solution becomes clear and then cooled to room temperature, excess hydrochloric acid is added to precipitate out, the precipitate is filtered, and the mixture is dried in a vacuum drying oven to obtain 180mg of compound 8.

200mg of Compound 8 are dissolved in 10ml of concentrated sulfuric acid and reacted at 60 ℃ for 5 hours. Pouring the reaction liquid into ice water, filtering out precipitate, and carrying out column chromatography to obtain 120mg of a product Comp-19, namely the compound shown in the formula i-1. 1H NMR (400MHz, TFA) δ 7.90(dd, J ═ 7.9,1.5Hz,2H),7.72(d, J ═ 1.5Hz,2H),7.37(d, J ═ 7.9Hz,2H), 7.21(s,2H),. EIMS m/z (%): calcd for c 2H 20H8b 2o2s2, 503.83; 503.83 is Found.

Example 22

Synthesis of 2, 9-dibromo-4, 11-dithothiochromeno [2,3-B ] thioxanthene-7, 14-dione Comp-20

In the same manner as in example 21, Compound 9 was used in place of Compound 6 to give Comp-20, a compound represented by formula K-1.

Example 23

Synthesis of phenylcarbazole-substituted dithiaanthrone derivatives Comp-21

Adding 200mg Comp-19 and 650mg N-phenyl-3-carbazole boric acid into a 250mL double-mouth bottle, adding 50mg tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, performing reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and performing column chromatography to obtain the dithio-anthrone derivative Comp-21

Example 24

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-22

Adding 200mg of 4, 11-dichloroothiochromeno [2,3-B ] thioxanthene-7, 14-dione and 650mg of 9-triphenylamine boric acid into a 250mL double-mouth bottle, adding 50mg of palladium tetratriphenylphosphine, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the dithio-anthrone derivative Comp-22

Example 25

Synthesis of phenylcarbazole, triphenylamine substituted dithiaanthrone derivative Comp-23

Adding 250mg of Comp-20 and 650mg of N-phenyl-3-carbazole boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, performing reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and performing column chromatography to obtain the chloro-dithio-anthrone derivative shown in formula 12.

Adding 350mg of compound 12 and 650mg of 9-triphenylamine boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain phenylcarbazole and triphenylamine substituted dithianone derivative Comp-23.

Example 26

Synthesis of triphenylamine-substituted dithiaanthrone derivative Comp-24

Adding 503mg of compound 13 and 636mg of 9-triphenylamine boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the triphenylamine substituted dithiaanthrone derivative Comp-24.

Example 27

Synthesis of carbazole, triphenylamine substituted dithiaanthrone derivative Comp-25

Weighing 572mg of compound 14 and 382mg of carbazole, adding the compound and the carbazole into a 100mL double-mouth bottle, adding 60mg of PEPSI-Ipr and 98mg of sodium tert-butoxide as catalysts and 10mL of anhydrous toluene solvent, carrying out reflux reaction for 24 hours under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain an intermediate compound 15.

Adding 744mg of compound 15 and 636mg of 9-triphenylamine boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the triphenylamine substituted dithiaanthrone derivative Comp-25.

Example 28

Synthesis of phenylcarbazole, triphenylamine substituted dithiaanthrone derivative Comp-26

Adding 572mg of compound 14 and 650mg of N-phenyl-3-carbazole boric acid into a 250mL double-mouth bottle, adding 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent, carrying out reflux reaction for 5h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the chloro-dithiaxanthone derivative shown in formula 16.

896mg of compound 16 and 650mg of 9-triphenylamine boric acid are added into a 250mL double-mouth bottle, 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent are added, reflux reaction is carried out for 5h under the protection of nitrogen, the solvent is removed under reduced pressure, dichloromethane and water are used for extraction, organic phases are combined, the solvent is evaporated to dryness under reduced pressure, and column chromatography is carried out to obtain phenylcarbazole and triphenylamine substituted dithianone derivative Comp-26.

Example 29

Synthesis of phenylcarbazole, triphenylamine and diphenyl-substituted dithianone derivatives Comp-27

1314mg of comp-26 was added to a 150ml two-necked flask, 10ml of glacial acetic acid was added, and 1ml of liquid bromine was added. The reaction mixture was heated to 120 ℃, reacted for 10 hours and then cooled to room temperature, and saturated sodium bisulfite solution was added to neutralize unreacted liquid bromine. Final filtration afforded compound 17.

1472mg of compound 17 and 400mg of biphenylyl boronic acid are added into a 250mL double-mouth bottle, 50mg of tetratriphenylphosphine palladium, 15mL of 2M potassium carbonate aqueous solution and 40mL of toluene solvent are added, reflux reaction is carried out for 5 hours under the protection of nitrogen, the solvent is removed under reduced pressure, dichloromethane and water are used for extraction, organic phases are combined, the solvent is evaporated to dryness under reduced pressure, and column chromatography is carried out to obtain the dithiaanthrone derivative Comp-27.

Example 30

An organic electroluminescent device was prepared using the derivative Comp-2 obtained in example 4;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

the glass with the anode is processedPlacing the substrate in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC20nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-2 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 10%, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 4.8V;

maximum luminance: 1203cd/m²；

Luminous efficiency: 0.55 cd/A.

FIG. 4 shows the electroluminescence spectrum at a certain voltage of an electroluminescent device based on Comp-2 doped TPBi as the light-emitting layer, the emission position being in the deep red/near infrared region; FIG. 5 shows the current density and luminance curves at different voltages for an electroluminescent device based on a Comp-2 doped TPBi as the light-emitting layer, the turn-on voltage of the display device being 4.8V and the maximum luminance being 1203cd/m²。

Example 31

An organic electroluminescent device was prepared using the derivative Comp-6 obtained in example 8;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC10nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-6 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 5%, and the total film thickness of the evaporation is 15 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the thickness of the evaporated film is 70 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (70nm)/EML (15nm)/mCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 3.8V;

maximum luminance: 9665cd/m²

Luminous efficiency: 12.7 cd/A.

FIG. 6 shows the electroluminescence spectrum at a certain voltage of an electroluminescent device based on a Comp-6 doped TPBi as the light-emitting layer, with emission sites in the orange-red region; FIG. 7 shows the current density and luminance curves at different voltages for an electroluminescent device based on a Comp-6 doped TPBi as the light-emitting layer, the turn-on voltage of the display device being 3.8V and the maximum luminance being 9665cd/m²。

Example 32

White organic electroluminescent devices were prepared using the derivative Comp-6 obtained in example 8;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, on the anode layer filmEvaporating TAPC10nm as a hole transport layer, and evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-6 doped 2SPAc-PPM blue light material on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 5%, and the total film thickness is 15 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 70 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (70nm)/EML (15nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 4.0V;

maximum luminance: 3000cd/m²；

Luminous efficiency: 10 cd/A.

Color rendering index: 75.

example 33

An organic electroluminescent device was prepared using the derivative Comp-1 obtained in example 3;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC20nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-1 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 5%, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 3.5V;

maximum luminance: 8800cd/m²；

Luminous efficiency: 38.2 cd/A;

external quantum efficiency: 15.9 percent.

Example 34

An organic electroluminescent device was prepared using the derivative Comp-13 obtained in example 15;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC20nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-13 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 8 percent, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 4.2V;

maximum luminance: 7400cd/m²；

Luminous efficiency: 36.5 cd/A;

example 35

An organic electroluminescent device was prepared using the derivative Comp-18 obtained in example 20;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC20nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-18 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 5%, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 3.8V;

maximum luminance: 9600cd/m²；

Luminous efficiency: 40.2 cd/A;

example 36

An organic electroluminescent device was prepared using the derivative Comp-21 obtained in example 23;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, firstly evaporating TAPC20nm as a hole transport layer on the anode layer film, and then evaporating mCP10nm as an exciton blocking layer;

continuously evaporating a layer of Comp-21 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 10%, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 4.0V;

maximum luminance: 5700cd/m²；

Luminous efficiency: 28.5 cd/A;

example 37

An organic electroluminescent device was prepared using the derivative Comp-23 obtained in example 25;

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, irradiating for 10 minutes by using an ultraviolet light cleaning machine, and bombarding by using a low-energy cation beam to show;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, depositing TAPC20nm on the anode layer film as hole transportEvaporating mCP10nm as exciton blocking layer;

continuously evaporating a layer of Comp-23 doped TPBi on the exciton blocking layer to be used as an organic light emitting layer of the device, wherein the doping proportion is 10%, and the total film thickness of the evaporation is 20 nm;

continuously evaporating a TMPYPB layer as an electron transmission layer of the device, wherein the total film thickness of the evaporation is 50 nm;

and finally, sequentially evaporating a LiF layer and Al on the electron transport layer to serve as a cathode layer of the device, wherein the thickness of the LiF layer is 1.0nm, and the thickness of the Al layer is 100 nm.

The device structure is Al (100nm)/LiF (1.0nm)/TMPYPB (50nm)/EML (20nm)/MCP (10nm)/TAPC (10nm)/ITO (100nm), as shown in FIG. 3;

the device performance index is as follows:

starting voltage: 3.9V;

maximum luminance: 5800cd/m²；

Luminous efficiency: 30.9 cd/A;

it should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (11)

1. The dithio-heteroanthrone derivative is characterized in that the general structural formula of the dithio-heteroanthrone derivative is shown as the following formula I:

wherein X is selected from a sulfur atom or a sulfone group; r₁、R₂And R₃Each independently selected from the group consisting of a hydrogen atom, an arylamine group of 6 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms,Substituted aryl of 6 to 30 carbon atoms, heterocyclic aryl of 5 to 50 carbon atoms, N-phenylcarbazolyl.

2. The dithiaanthrone derivative according to claim 1, wherein said arylamino group having 6 to 30 carbon atoms is selected from a dianilino group or a triphenylamine group.

3. The dithianone derivative according to claim 1, wherein said aryl group having 6 to 30 carbon atoms is selected from one of phenyl, perylenyl, pyrenyl, diphenyl, triphenyl, and tetracenyl.

4. The dithianone derivative according to claim 1, wherein said substituted aryl group having 6 to 30 carbon atoms is one selected from the group consisting of o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o-cumyl group, m-cumyl group, p-cumyl group and tritolyl group.

5. The dithiaanthrone derivative of claim 1, wherein said heteroaryl group having 5 to 50 carbon atoms is selected from the group consisting of 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-benzofuryl, and mixtures thereof, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, dibenzofuran-2-yl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-carbazolyl, 2-quinoxalyl, 3-quinolyl, 4-isoquinolyl, 5-quinolyl, 6-isoquinolyl, 6-quinoxalyl, 1-carbazolyl, 5-quinoxalyl, 3-isobenzofuranyl, 6-quinolyl, 4-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 6-quinolyl, 5-quinolyl, 1-isobenzofuranyl, 6-yl, 5-quinolyl, 3-isobenzofuranyl, 3-yl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 3-quinolyl, and a, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 1, 7-phenanthroline-2-yl, 1, 7-phenanthroline-3-yl, 1, 7-phenanthroline-4-yl, 1, 7-phenanthroline-5-yl, 1, 7-phenanthroline-6-yl, 1, 7-phenanthroline-8-yl, 1, 7-phenanthroline-9-yl, 1, 7-phenanthroline-10-yl group, 1, 8-phenanthroline-2-yl group, 1, 8-phenanthroline-3-yl group, 1, 8-phenanthroline-4-yl group, 1, 8-phenanthroline-5-yl group, 1, 8-phenanthroline-6-yl group, 1, 8-phenanthroline-7-yl group, 1, 8-phenanthroline-9-yl group, 1, 8-phenanthroline-10-yl group, 1, 9-phenanthroline-2-yl group, 1, 9-phenanthroline-3-yl group, 1, 9-phenanthroline-4-yl group, 1, 9-phenanthroline-5-yl group, 1, 9-phenanthroline-6-yl group, 1, 9-phenanthroline-7-yl group, 1, 9-phenanthroline-8-yl group, 1, 9-phenanthroline-10-yl group, 1, 10-phenanthroline-2-yl group, 1, 10-phenanthroline-3-yl group, 1, 10-phenanthroline-4-yl group, 1, 10-phenanthroline-5-yl group, 2, 9-phenanthroline-1-yl group, 2, 9-phenanthroline-3-yl group, 2, 9-phenanthroline-4-yl group, 2, 9-phenanthroline-5-yl group, 2, 9-phenanthroline-6-yl group, 2, 9-phenanthroline-7-yl group, 2, 9-phenanthroline-8-yl group, 2, 9-phenanthroline-10-yl group, 2, 8-phenanthroline-1-yl group, 2, 2, 8-phenanthroline-3-yl group, 2, 8-phenanthroline-4-yl group, 2, 8-phenanthroline-5-yl group, 2, 8-phenanthroline-6-yl group, 2, 8-phenanthroline-7-yl group, 2, 8-phenanthroline-9-yl group, 2, 8-phenanthroline-10-yl group, 2, 7-phenanthroline-1-yl group, 2, 7-phenanthroline-3-yl group, 2, 7-phenanthroline-4-yl group, 2, 7-phenanthroline-5-yl group, 2, 7-phenanthroline-6-yl group, 2, 7-phenanthroline-8-yl group, 2, 7-phenanthroline-9-yl group, 2, 7-phenanthroline-10-yl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, dibenzothiophen-2-yl group.

6. A process for the synthesis of the dithiaanthrone derivatives according to any one of claims 1 to 5,

when the dithiaanthrone derivative has the general structural formula as shown in formula I:

when R is₁、R₃Is a hydrogen atom, R₂When not hydrogen atom, the synthesis method comprises the following steps: a compound of formula a and a compound having R₂Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₂Carrying out Ullmann reaction on a nitrogen-containing heterocyclic compound of a substituent group to obtain a compound with a structural formula shown as a formula I-1;

or

When R is₁Is a hydrogen atom, R₂、R₃When not hydrogen atom, the synthesis method comprises the following steps: mixing a compound shown as a formula I-1 with liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula b; a compound of the formula b and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-2;

or

When R is₁Not being a hydrogen atom, R₂、R₃When the hydrogen atom is used, the synthesis method comprises the following steps: a compound of the formula c and a compound having R₁Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₁Carrying out Ullmann reaction on a nitrogen-containing heterocyclic compound of a substituent group to obtain a compound with a structural formula shown as a formula I-3;

or

When R is₁、R₃Not being a hydrogen atom, R₂When the hydrogen atom is used, the synthesis method comprises the following steps: a compound of formula I-3 and liquid bromine in glacial acetic acidMixing, heating and reacting to generate a compound shown in a formula d; compounds of formula d and having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-4;

or

When R is₁、R₂、R₃And when the hydrogen atom is simultaneously used, the structural formula of the compound shown in the formula I is shown as a formula I-5:

wherein, when X is a sulfur atom, the synthesis method comprises the following steps:

reacting to generate a compound shown as a formula I-5-1,

when X is sulfuryl, the synthesis method comprises the following steps:

dissolving the compound shown as the formula I-5-1 in dichloromethane under the condition of ice-water bath, adding m-chloroperoxybenzoic acid, reacting at room temperature to obtain the compound shown as the formula I-5-2,

or

When R is₁、R₂And at the same time being a hydrogen atom, R₃When not hydrogen atom, the synthesis method comprises the following steps: a compound of formula I-5 and liquid bromineMixing glacial acetic acid, and heating for reaction to generate a compound shown as a formula e; a compound of the formula e and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain a compound with a structural formula shown as a formula I-6;

or

When R is₁、R₂While not being a hydrogen atom, R₃When the hydrogen atom is used, the synthesis method comprises the following steps: a compound of the formula f with a compound having R₂Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₂Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula g; a compound of the formula g with a compound having R₁Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₁Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula I-7,

or

When R is₁、R₂、R₃Meanwhile, when the hydrogen atom is not contained, the synthesis method comprises the following steps: mixing the compound shown as the formula I-7 with liquid bromine in glacial acetic acid, and heating for reaction to generate a compound shown as a formula h; a compound of the formula h and a compound having R₃Suzuki reaction of substituted boronic acid or boronic acid pinacol ester or reaction with R-bearing₃Carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to generate a compound shown as a formula I-8,

formula I-8.

7. The method of synthesis according to claim 6,

when X is a sulfur atom, the sulfur atom,

the synthesis process of the compound shown in the formula a is as follows:

the synthesis process of the compound shown in the formula c is as follows:

the synthesis process of the compound shown as the formula I-5-1 comprises the following steps:

the synthesis process of the compound shown in the formula f is as follows:

when X is a sulfone group, the compound is,

the compounds of formula a, formula c and formula f are each:

the compounds shown in the formula a-2, the formula c-2 and the formula f-2 are obtained by respectively dissolving the compounds shown in the formula a-1, the formula c-1 and the formula f-1 in dichloromethane under the condition of ice-water bath, adding m-chloroperoxybenzoic acid, and reacting at room temperature.

8. Use of the dithiaanthrone derivatives as claimed in any one of claims 1 to 5 for the preparation of organic electroluminescent devices.

9. Use according to claim 8, wherein the organic electroluminescent device is an organic electroluminescent device based on thermally activated delayed fluorescence.

10. Use according to claim 8, wherein the organic electroluminescent device is a white organic electroluminescent device.

11. The use according to claim 8, wherein the dithianone derivative is used in the light-emitting layer of an organic electroluminescent device.

Images